Paraxylene Separation Process

ABSTRACT

The invention relates to a p-xylene separation process wherein at least a portion of ethylbenzene present in an aromatics-containing feed is removed prior to isomerization. Aspects of the invention provide a process for producing p-xylene. The process includes providing a first mixture comprising ≧5.0 wt. % of aromatic C 8  isomers, the C 8  isomers comprising p-xylene and ethylbenzene. A p-xylene-containing portion and an ethylbenzene-containing portion are separated from the first mixture in a first separation stage to form a p-xylene-depleted raffinate. The first separation stage can include at least one simulated moving-bed adsorptive separation stage. At least a portion the p-xylene-depleted raffinate in the liquid phase is reacted to produce a reactor effluent comprising aromatic C 8  isomers. The first mixture can be combined with ≧50.0 wt. % of the reactor effluent&#39;s aromatic C 8  isomers. The combining can be carried out before and/or during the separating of the p-xylene and ethylbenzene portions.

PRIORITY

This application claims priority to U.S. patent Application No.61/955,907, filed Mar. 20, 2014, and EP 14167834.2 filed May 12, 2014,the disclosures of which are incorporated in their entireties.

FIELD OF INVENTION

Aspects of the invention relate to para-xylene (p-xylene) separationprocesses. In particular, aspects of the invention relate to xylene loopprocesses.

BACKGROUND OF INVENTION

Aromatic hydrocarbons, such as benzene, toluene, xylene, etc. are usefulas fuels, solvents, and as feeds for various chemical processes. Of thexylenes, para-xylene is particularly useful for manufacturing phthalicacids such as terephthalic acid, which is an intermediate in themanufacture of synthetic fibers such as polyester fibers. Xylenes can beproduced from naphtha, e.g., by catalytic reforming, with the reformateproduct containing a mixture of xylene isomers and ethylbenzene.Separating p-xylene from the mixture generally requires stringentseparations, e.g., separations utilizing superfractionation andmultistage refrigeration steps. Such separations are characterized bycomplexity, high energy-usage, and high cost.

Chromatographic separation is an alternative to more stringentseparations, such as superfractionation, for removing p-xylene from amixture of aromatic C₈ isomers.

Chromatographic separation involves simulating a moving bed of selectiveadsorbent. Examples of commercial processes in which p-xylene isseparated from aromatic C₈ isomers by simulated moving-bed separationinclude PAREX, available from UOP, ELUXYL, available from Axens, andAROMAX, available from Toray. Although a raffinate depleted in p-xylenecan be recycled as a feed component to the p-xylene separation step,ethylbenzene will undesirably accumulate in the recycle stream.

In order to overcome this difficulty, p-xylene is conventionallyproduced in a continuous process (commonly referred to as a xyleneloop), in which p-xylene-depleted raffinate is isomerized to reduce theamount of ethylbenzene therein. The isomerization reduces the amount ofethylbenzene in the stream by converting it into an equilibrium ornear-equilibrium xylene mixture, e.g., a mixture comprising xyleneisomers; diethylbenzene; benzene; and non-aromatics such as C₂-C₆olefins and C₁-C₆ paraffins. One such process involves (a) providing amixture of aromatic C₈ isomers containing p-xylene, (b) separating fromthe C₈ isomers a high-purity p-xylene extract and a p-xylene-depletedraffinate by simulated moving bed adsorption, crystallization, or acombination thereof, (c) catalytically isomerizing the p-xylene-depletedraffinate to produce an isomerate, and (e) recycling the isomerate tostep (a).

Vapor-phase isomerization of the raffinate's ethylbenzene is generallyneeded to achieve an ethylbenzene content of ≦10.0 mole % ethylbenzeneper mole of isomerate. However, vapor-phase isomerization has manydisadvantages, including high energy consumption, costly and complexprocess equipment, and high xylenes loss due to conversion of thexylenes in the raffinate into undesirable products such as light gasesand heavy aromatics, e.g., by one or more side-reactions such as one ormore of cracking, transalkylation, or disproportionation. Attempts toovercome these disadvantages include reducing the quantity of raffinategoing to the vapor-phase isomerization, e.g., removing ethylbenzene fromthe raffinate by (i) superfractionation, as disclosed in French PatentFR-A-2792632, or (ii) using chromatographic ethylbenzene separation inthe p-xylene separation stage, as disclosed in U.S. Pat. No. 7,915,471.The separated ethylbenzene is isomerized in a vapor-phase isomerizationstage, with the remainder of the raffinate being isomerized in aliquid-phase isomerization stage. The liquid-phase isomerization stageis operated under conditions which lessen undesired cracking,transalkylation, and disproportionation side-reactions. Isomerates fromthe vapor-phase and liquid-phase isomerization stages are then combinedand recycled to stage (a) of the xylene loop.

Even when ethylbenzene is separated for vapor-phase isomerization, withthe remainder of the p-xylene-depleted raffinate subjected toliquid-phase isomerization, the vapor-phase isomerization stagecontributes to xylene-loop inefficiencies. Some of these inefficienciesresult from one or more of (i) the need to vaporize the separatedethylbenzene and then re-condense the vapor-phase isomerate forcombining with the isomerate derived from the liquid-phase isomerizationstage, (ii) the need to separate unreacted molecular hydrogen vapor forre-use as an isomerization treat gas, and (iii) the need for removingnon-aromatics formed during isomerization. Consequently, it is desiredto further lessen or even eliminate the need for vapor-phaseisomerization.

SUMMARY OF INVENTION

It has been found that xylene loop efficiency is unexpectedly improvedby separating and removing from the loop at least a portion of theethylbenzene present in the feed to the p-xylene separation stage and/orat least a portion of the non-aromatics present in the feed to thep-xylene separation stage, the ethylbenzene and/or non-aromatics removalbeing carried out upstream of raffinate isomerization. Separating andconducting away from the xylene loop at least a portion of theethylbenzene increases xylene loop energy efficiency, e.g., by lesseningthe number of Joules consumed by the xylene loop to produce one kilogramof p-xylene by ≧20%, e.g., ≧25% when ≧90 wt. % of ethylbenzene presentin the feed to the p-xylene separation stage is removed upstream of theisomerization. Moreover, removing at least a portion of the xyleneloop's ethylbenzene decreases the xylene loop's complexity, e.g., bylessening or even eliminating the need for an energy-intensive andcomplex vapor-phase isomerization downstream of p-xylene separation. Theethylbenzene can be removed in the p-xylene separation stage, e.g., as acomponent of a second raffinate that is chromatographically separated inthe p-xylene separation stage. It is also advantageous to remove atleast a portion of any non-aromatics from the xylene loop, e.g.,removing non-aromatics upstream of raffinate isomerization. Theadvantages can be attained even in aspects where ethylbenzene is notremoved. Certain advantages result from the relatively high-value ofgasoline boiling-range non-aromatics (e.g., those having anatmospheric-pressure boiling point in the range of from 30° F. to 430°F.), which can be removed from the loop for use in higher-value uses,e.g., as a blendstock for transportation fuels. Removing non-aromaticsis also advantageous because doing so lessens the amount of hydrogenutilized in the process, and the associated compression costs.

In certain aspects, the invention relates to a process for producingp-xylene, the process comprising, (a) providing a first mixturecomprising ≧5.0 wt. % of aromatic C₈ isomers, based on the weight of thefirst mixture, said aromatic C₈ isomers comprising p-xylene andethylbenzene; (b) separating a p-xylene-containing portion and anethylbenzene-containing portion from the first mixture in a firstseparation stage to form a p-xylene-depleted raffinate, wherein thefirst separation stage optionally includes at least one simulatedmoving-bed adsorptive separation stage; (c) reacting at least a portionthe p-xylene-depleted raffinate in the liquid phase to produce a reactoreffluent comprising aromatic C₈ isomers; and (d) combining with thefirst mixture ≧50.0 wt. %, preferably ≧90.0 wt. %, of the reactoreffluent's aromatic C₈ isomers, preferably p-xylene, based on the weightof the reactor effluent's aromatic C₈ isomers, the combining beingcarried out before and/or during the separating of (b). At least part ofthe separated ethylbenzene-containing portion is conducted away.

A particular aspect relates to a process for producing p-xylene, theprocess comprising providing a first mixture comprising ≧5.0 wt. % ofaromatic C₈ isomers, based on the weight of the first mixture, said C₈isomers comprising p-xylene and ethylbenzene. The following componentsof the first mixture are separated in a first separation stage: (i) ap-xylene-depleted raffinate; (ii) a p-xylene-containing portioncomprising ≧10.0 wt. % of the first mixture's p-xylene, based on theweight of the first mixture's p-xylene; and (iii) anethylbenzene-containing portion comprising ≧10.0 wt. % of the firstmixture's ethylbenzene, based on the weight of the first mixture'sethylbenzene. At least a portion of the p-xylene-containing portion isconducted away from the process, as is ≧50.0 wt. % of theethylbenzene-containing portion, based on the weight of theethylbenzene-containing portion. The process continues by isomerizing atleast a portion the p-xylene-depleted raffinate in the liquid phasewherein ≦10.0 wt. %, e.g., ≦1.0 wt. % or ≦0.1 wt. %, of thep-xylene-depleted raffinate is in the vapor phase during theisomerizing, the weight percent being based on the weight of thep-xylene-depleted raffinate. The isomerizing produces a reactor effluentcomprising ≧90.0 wt. % p-xylene, based on the weight of the reactoreffluent's aromatic C₈ isomers. At least a portion of the reactoreffluent is combined with the first mixture, the combining being carriedout before and/or during the separating in the first separation stage.

In other aspects, the invention relates to an improved xylene loop,wherein the xylene loop comprises (a) providing a first mixturecomprising aromatic C₈ isomers; (b) separating from the first mixture ina first stage: (i) a p-xylene-depleted raffinate; (ii) ap-xylene-containing portion comprising ≧10.0 wt. % of the mixture'sp-xylene, based on the weight of the mixture's p-xylene; and (iii) anethylbenzene-containing portion comprising ≧10.0 wt. % of the mixture'sethylbenzene, based on the weight of the mixture's ethylbenzene; whereinthe first separation stage includes at least one simulated moving-bedadsorption chromatographic separation; (c) conducting away at least aportion of the separated p-xylene; (d) reacting at least a portion thep-xylene-depleted raffinate in the liquid phase to produce a reactoreffluent comprising aromatic C₈ isomers; and (e) recycling to step (b)≧50.0 wt. % of aromatic C₈ isomers of the reactor effluent, based on theweight of the aromatic C₈ isomers in the reactor effluent. Theimprovement comprises: (f) conducting away from the xylene loop ≧50.0wt. % of the ethylbenzene separated in step (c), based on the weight ofthe separated ethylbenzene; and (g) exposing ≦10.0 wt. % of aromatic C₈isomers in the xylene loop to vapor-phase isomerization, based on theweight of aromatic C₈ isomers in the xylene loop.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a p-xylene separation process according to an aspectof the invention.

FIG. 2 illustrates a p-xylene separation process according to aspects ofthe invention including a second separation stage wherein at least aportion of any C₁-C₇ compounds are removed from the reactor effluent.

FIG. 3 illustrates a p-xylene separation process according to aspects ofthe invention. The separation process includes removing one or moreby-products from the first mixture and/or providing the C₈₊ hydrocarbonsto a third separation stage 301.

FIG. 4 illustrates another aspect of a p-xylene separation processaccording to the invention.

DETAILED DESCRIPTION

The following description relates to aspects of the invention whichinclude removing ethylbenzene from a xylene loop upstream ofisomerization. The invention is not limited to these aspects, and is notmeant to foreclose other aspects within the broader scope of theinvention, such as those which include non-aromatics separation. FIG. 1schematically illustrates a process 100 which features certain aspectsof the invention. First mixture 101 is passed to first separation stage102 where a p-xylene-containing portion 103 and anethylbenzene-containing portion 104 are separated and conducted away, inorder to produce a p-xylene-depleted raffinate 105 for theisomerization. First mixture 101 typically comprises ≧5.0 wt. % ofaromatic C₈ isomers, based on the weight of the first mixture, saidaromatic C₈ isomers comprising p-xylene and ethylbenzene. Generally, thecontent of aromatic C₈ isomers in first mixture 101 may range from 5.0to 100.0 wt. %. The lower limit on the content of aromatic C₈ isomers infirst mixture 101 may be 5.0 wt. %, 10.0 wt. %, 20.0 wt. %, 30.0 wt. %,40.0 wt. %, 50.0 wt. %, 60.0 wt. %, 70.0 wt. %, 80.0 wt. %, 90.0 wt. %,95.0 wt. %, 99.0 wt. %, or 100.0 wt. %. The upper limit on the contentof aromatic C₈ isomers in first mixture 101 may be 5.0 wt. %, 10.0 wt.%, 20.0 wt. %, 30.0 wt. %, 40.0 wt. %, 50.0 wt. %, 60.0 wt. %, 70.0 wt.%, 80.0 wt. %, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %.Aspects expressly described herein include those where any lower limitis combined with any upper limit. In particular aspects, first mixture101 comprises ≧50.0 wt. %. e.g., ≧60.0 wt. %, ≧65.0 wt. %, ≧70.0 wt. %,≧75.0 wt. %, ≧80.0 wt. %, ≧85.0 wt. %, ≧90.0 wt. %, 95.0 wt. %, ≧99.0wt. %, of a mixture of p-xylene, ethylbenzene, meta-xylene (m-xylene),and ortho-xylene (o-xylene), based on the weight of the first mixture101.

The first separation stage 102 is typically a simulated moving bedabsorptive separation unit having solvent (sometimes referred to as“desorbant”) circulating therethrough via line 106. The circulation canbe carried out using one or more pumps, such as the pump shownschematically in FIG. 1 as a component of stage 102. In particularaspects the first separation stage 102 is a chromatographic separationstage. Solvent 106 should be selected to separate under the separationconditions, e.g., solvent flow, temperature, etc., the components offirst mixture 101 as desired. Typical solvents include hydrocarbonsolvents, e.g., toluene. Exemplary separation processes are described inU.S. Pat. No. 7,915,471, incorporated herein by reference in itsentirety.

Separation stage 102 should be operated such that p-xylene-containingportion 103 comprises ≧10.0 wt. % of the first mixture's p-xylene, basedon the weight of the first mixture's p-xylene. Generally, the content ofp-xylene in p-xylene-containing portion 103 may range from 10.0 to 100.0wt. % of the first mixture's p-xylene. The lower limit on the content ofp-xylene in the p-xylene-containing portion 103 may be 10.0 wt. %, 20.0wt. %, 30.0 wt. %, 40.0 wt. %, 50.0 wt. %, 60.0 wt. %, 70.0 wt. %, 80.0wt. %, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %. The upperlimit on the content of p-xylene in p-xylene-containing portion 103 maybe 10.0 wt. %, 20.0 wt. %, 30.0 wt. %, 40.0 wt. %, 50.0 wt. %, 60.0 wt.%, 70.0 wt. %, 80.0 wt. %, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0wt. %. Aspects expressly described herein include those where any lowerlimit is combined with any upper limit. In particular aspects,p-xylene-containing portion 103 comprises 10.0 to 75.0 wt. %, 10.0 to65.0 wt. %, 10.0 to 50.0 wt. %, 10.0 to 40.0 wt. %, 10.0 to 30.0 wt. %,or 10.0 to 20.0 wt. % of the first mixture's p-xylene. In some aspects,p-xylene-containing portion 103 comprises 20.0 to 75.0 wt. %, 30.0 to 75wt. %, 40.0 to 75 wt. %, 50.0 to 75.0 wt. %, or 65.0 to 75.0 wt. % ofthe first mixture's p-xylene. In particular aspects, least a portion ofthe p-xylene-containing portion 103 is conducted away from the process100. In certain aspects, 10.0 to 100.0 wt. %, e.g., 40.0 to 100.0 wt. %,50.0 to 100.0 wt. %, 60.0 to 100.0 wt. %, 70.0 to 100.0 wt. %, 80.0 to100.0 wt. %, 80.0 to 100.0 wt. %, or 95.0 to 100.0 wt. %, of thep-xylene portion is conducted away from the process.

Ethylbenzene is separated and removed from process 100 viaethylbenzene-containing portion 104, which typically comprisescomprising ≧10.0 wt. % of the first mixture's ethylbenzene, based on theweight of the first mixture's ethylbenzene. The lower limit on thecontent of ethylbenzene in the ethylbenzene-containing portion 104 maybe 10.0 wt. %, 20.0 wt. %, 30.0 wt. %, 40.0 wt. %, 50.0 wt. %, 60.0 wt.%, 70.0 wt. %, 80.0 wt. %, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0wt. %. The upper limit on the content of ethylbenzene inethylbenzene-containing portion 104 may be 10.0 wt. %, 20.0 wt. %, 30.0wt. %, 40.0 wt. %, 50.0 wt. %, 60.0 wt. %, 70.0 wt. %, 80.0 wt. %, 90.0wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %. Aspects expresslydescribed herein include those where any lower limit is combined withany upper limit. Generally, ethylbenzene-containing portion 104comprises 10.0 to 75.0 wt. %, 10.0 to 65.0 wt. %, 10.0 to 50.0 wt. %,10.0 to 40.0 wt. %, 10.0 to 30.0 wt. %, or 10.0 to 20.0 wt. % of thefirst mixture's ethylbenzene. In certain aspects,ethylbenzene-containing portion 104 comprises 20.0 to 75.0 wt. %, 30.0to 75.0 wt. %, 40.0 to 75 wt. %, 50.0 to 75.0 wt.%, or 65.0 to 75.0 wt.% of the first mixture's p-xylene. Removing at least a portion of theethylbenzene from the process decreases the xylene loop's complexity,e.g., by lessening or even eliminating the need for an energy-intensiveand complex vapor-phase isomerization downstream of p-xylene separation.The ethylbenzene can be removed in the p-xylene separation stage, e.g.,as a component of a second extract. The second extract can bechromatographically separated in the p-xylene separation stage, asdisclosed in U.S. Pat. No. 7,915,471. In particular aspects, at least aportion of the ethylbenzene-containing portion 104 is conducted awayfrom the process 100, e.g., ≧10.0 wt. % of the ethylbenzene-containingportion is conducted away, based on the weight of theethylbenzene-containing portion. In certain aspects, 10.0 to 100.0 wt.%, e.g., 40.0 to 100.0 wt. %, 50.0 to 100.0 wt. %, 60.0 to 100.0 wt. %,70.0 to 100.0 wt. %, 80.0 to 100.0 wt. %, 80.0 to 100.0 wt. %, or 95.0to 100.0 wt. %, of ethylbenzene-containing portion 104 is conducted awayfrom the process. Since at least part of the first mixture'sethylbenzene is separated and conducted away, the process generallyincludes isomerizing <90.0 wt. % of the first mixture'sethylbenzene,e.g., ≦50.0 wt. %, such as ≦25.0 wt. %. In certain aspects,the process includes isomerizing ≦10.0 wt. % of the first mixture'sethylbenzene, e.g., ≦5.0 wt. %, such as ≦1.0 wt. ≦1.0 wt. %.

The process may include separating at least a portion of anynon-aromatic hydrocarbon molecules from the first mixture 101. This canbe done upstream of stage 107, e.g., in stage 102 (not shown). Firstseparation stage 102 may remove from 5.0 to 100 wt. % of anynon-aromatic hydrocarbons, based on the amount of such hydrocarbons inthe first mixture. In particular aspects, the first separation stage 102removes ≧50.0 wt. %, preferably ≧75.0 wt. %, or ≧90.0 wt. % of thenon-aromatic hydrocarbons. Certain non-aromatic hydrocarbon molecules,e.g., C₉ non-aromatic molecules, have approximately the same volatilityas p-xylene. It is conventional to ameliorate problems associated withnon-aromatics separation from the xylene loop by cracking at least aportion of the non-aromatics during xylene isomerization. This approachlessens xylene loop efficiency (as a result of, e.g., bottlenecking ofthe isomerization stage), and leads to an increase in separationcomplexity as a result of the need to remove the cracked products. Ithas been found that this difficulty can be overcome by removing at leasta portion of the non-aromatics upstream of the isomerization, e.g., byremoving non-aromatics from the first mixture in the first separationstage. As in the case of ethylbenzene removal, separation ofnon-aromatics can be carried out using at least one simulated moving-bedadsorption chromatographic separation. Advantageously, non-aromaticsseparation and ethylbenzene separation can be carried out in the samesimulated moving-bed adsorption chromatographic separation using thesame desorbent. The chromatographic separation can be carried out usingconventional methods, such as those described in U.S. Pat. No.3,662,020, which is incorporated by reference herein in its entirety.One or more conventional desorbents can be used, e.g., toluene.Conventional configurations can be utilized for the simulated moving-bedadsorption chromatographic separation of the first separation stage,e.g., stacked-bed mode and/or multiple bed mode. Suitable configurationsare disclosed in U.S. Pat. Nos. 2,985,589 and 3,310,486, which areincorporated by reference herein in their entirety. In certain aspects,four streams are conducted away from the first separation stage: (i)first and second extracts and (ii) first and second raffinates.Referring again to FIG. 1, the first extract corresponds to thep-xylene-containing portion removed from stage 102. The second extractcorresponds to the ethylbenzene portion removed from stage 102. Thefirst raffinate comprises at least a portion of the first mixture'sm-xylene and o-xylene, e.g., ≧50.0 wt. % of the first mixture's m-xyleneand ≧50.0 wt. % of the first mixture's o-xylene. The second raffinatecomprises non-aromatics, e.g., ≧50.0 wt. % of the first mixture'snon-aromatics. Although it is not required, the invention is compatiblewith removing at least a portion of any desorbent from one or more ofthe first extract, second extract, first raffinate, and secondraffinate. For example, desorbent can be removed from the firstraffinate upstream of the isomerization in order to further debottleneckthe isomerizing. Since at least part of the first mixture'snon-aromatics can be separated and conducted away, the processoptionally includes subjecting to isomerization conditions <90.0 wt. %of the first mixture's non-aromatics, e.g., ≦50.0 wt. %, such as ≦25.0wt. %. In certain aspects, the process includes subjecting ≦10.0 wt. %of the first mixture's non-aromatics to isomerization conditions, ≦5.0wt. %, such as ≦1.0 wt. %.

The p-xylene-depleted raffinate 105 is provided to reactor 107 whereraffinate 105 is reacted in the liquid phase to produce a reactoreffluent comprising aromatic C₈ isomers. Reactor 107 may be any type ofreactor or reactor process suitable for increasing the amount of C₈isomers, relative to the amount of aromatic C₈ isomers in raffinate 105.Reactor 107 typically performs at least one of (i) one or more reformingreactions, (ii) one or more disproportionation reactions, (iii) one ormore transalkylation reactions, and (iv) one or more cracking reactions.While the reaction processes in reactor 107 are conducted in the liquidphase, some of raffinate 105 may be in the vapor phase. Thus, inparticular aspects, ≦10.0 wt. %, e.g., ≦7.5 wt. %, ≦5.0 wt. %, ≦2.5 wt.%, ≦1.0 wt. %, ≦0.5 wt. %, −0.2 wt. %, ≦0.1 wt. %, of thep-xylene-depleted raffinate 105 in reactor 107 is in the vapor phaseduring the reacting, the weight percent being based on the weight of thep-xylene-depleted raffinate 105.

Reactor effluent 108 generally comprises products formed in reactor 107,and can also include unreacted raffinate. For example, reactor effluent108 can comprise C₁-C₇ compounds, C₈ aromatic isomers, and C₉₊aromatics. In certain aspects, the concentration of p-xylene in effluent108 may be suitable for use in other processes or it may be sent forfurther purification and/or isolation of the p-xylene. In certainaspects, at least a portion of the reactor effluent 108 is recycledthrough line 109 to be combined with the first mixture 101. Anydesirable amount of reactor effluent may be recycled through line 109.Typically, ≧50.0 wt. %, of the aromatic C₈ isomers of the reactoreffluent 108, based on the total amount of aromatic C₈ isomers inreactor effluent 108, are recycled for combining with the first mixture101. The lower limit on the amount of aromatic C₈ isomers recycled forcombining with the first mixture 101 may be 50.0 wt. %, 55.0 wt. %, 60.0wt. %, 65.0 wt. %, 70.0 wt. %, 75.0 wt. %, 80.0 wt. %, 85.0 wt. %, 90.0wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %. The upper limit on theamount of aromatic C₈ isomers recycled for combining with the firstmixture 101 may be 50.0 wt. %, 55.0 wt. %, 60.0 wt. %, 65.0 wt. %, 70.0wt. %, 75.0 wt. %, 80.0 wt. %, 85.0 wt. %, 90.0 wt. %, 95.0 wt. %, 99.0wt. %, or 100.0 wt. %. Any combination of lower and upper limits on theamount of aromatic C₈ isomers recycled for combining with the firstmixture 101 is expressed disclosed. In particular aspects, the aromaticC₈ isomers recycled through line 109 comprise ≧50.0 wt. % (e.g., ≧50.0wt. %, ≧55.0 wt. %, ≧60.0 wt. %, ≧65.0 wt. %, ≧70.0 wt. %, ≧75.0 wt. %,≧80.0 wt. %, ≧85.0 wt. %, ≧90.0 wt. %, ≧95.0 wt. %, ≧99.0 wt. %, xyleneisomers (e.g., o-xylene, m-xylene, p-xylene). In particular aspects, thexylene isomers comprise ≧50.0 wt. %, ≧55.0 wt. %, ≧60.0 wt. %, ≧65.0 wt.%, ≧70.0 wt. %, ≧75.0 wt. %, ≧80.0 wt. %, ≧85.0 wt. %, ≧90.0 wt. %,≧95.0 wt. %, ≧99.0 wt. %, p-xylene. Line 109 typically provides thearomatic C₈ isomers before and/or during the separating of (b).

With continuing reference to FIG. 1, FIG. 2 illustrates process 200.Process 200 includes providing the reactor effluent 108 to a secondseparation stage 201 wherein at least a portion of one or more C₁-C₇compounds in the reactor effluent 108 are separated via line 202.Particular aspects of process 200 include conducting the separated oneor more C₁-C₇ compounds away from the process. Heavier compounds,including aromatic C₈ isomers and C₉₊hydrocarbons, exit secondseparation stage 201 via line 203. Separation stage 201 may be anyseparation means suitable for separating C₁-C₇ compounds from C₈₊hydrocarbons. In particular aspects, separation stage 201 is astabilization column or distillation column. Typically, the C₁-C₇compounds are separated in separation stage 201 before the reactoreffluent 108 is recycled for combining with the first mixture 101, asshown in FIG. 2. In other words, the C₁-C₇ compounds are separated andat least a portion of the C₈₊ hydrocarbons of line 203 are recycledthrough line 204 to be combined with first mixture 101. Any desirableamount of the C₈₊ hydrocarbons exiting separation stage 201 via line 203may be recycled through line 204. Typically, ≧50.0 wt. %, of the C₈₊hydrocarbons of the separation stage 201, based on the total amount ofC₈₊ hydrocarbons exiting separation stage 201, are recycled forcombining with the first mixture 101. The lower limit on the amount ofC₈₊ hydrocarbons recycled for combining with the first mixture 101 maybe 10.0 wt. %, 20.0 wt. %, 30.0 wt. %, 40.0 wt. %, 50.0 wt. %, 55.0 wt.%, 60.0 wt. %, 65.0 wt. %, 70.0 wt. %, 75.0 wt. %, 80.0 wt. %, 85.0 wt.%, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %. The upper limiton the amount of C₈₊ hydrocarbons recycled for combining with the firstmixture 101 may be 10.0 wt. %, 20.0 wt. %, 30.0 wt. %, 40.0 wt. %, 50.0wt. %, 55.0 wt. %, 60.0 wt. %, 65.0 wt. %, 70.0 wt. %, 75.0 wt. %, 80.0wt. %, 85.0 wt. %, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %.Any combination of lower and upper limits on the amount of C₈₊hydrocarbons recycled for combining with the first mixture 101 isexpressed disclosed. In particular aspects, the C₈₊ hydrocarbonsrecycled through line 204 comprise ≧50.0 wt. % (e.g., ≧50.0 wt. %, ≧55.0wt. %, ≧60.0 wt. %, ≧65.0 wt. %, ≧70.0 wt. %, ≧75.0 wt. %, ≧80.0 wt. %,≧85.0 wt. %, ≧90.0 wt. %, ≧95.0 wt. %, ≧99.0 wt. %), C₈₊ aromatichydrocarbons (e.g., ethylbenzene, o-xylene, m-xylene, p-xylene). Inparticular aspects, the aromatic C₈₊ hydrocarbons recycled via line 204comprise ≧50.0 wt. %, ≧55.0 wt. %, ≧60.0 wt. %, ≧65.0 wt. %, ≧70.0 wt.%, ≧75.0 wt. %, ≧80.0 wt. %, ≧85.0 wt. %, ≧90.0 wt. %, ≧95.0 wt. %,≧99.0 wt. %, p-xylene.

With continuing reference to FIGS. 1 and 2, FIG. 3 illustrates anexemplary process 300. Optionally, process 100 or process 200 mayinclude removing one or more by-products from the first mixture and/orproviding at least a portion of any C₈₊ hydrocarbons exiting theseparation stage 201 to a third separation stage 301 via line 203.Optionally, the portion of C₈₊ hydrocarbon can be derived from a fourthseparation stage 304. Stage 304 can be located downstream of stage 201,as shown in the figure. For example, in process 300, first mixture 101may be passed to third separation stage 301, wherein at least a portionof a by-product, e.g., o-xylene and/or any C₉₊ aromatics in the firstmixture are removed via line 303. The remainder is passed to the firstseparation stage 102. The amount of the one or more by-products removedin the separation stage 301 may be 5.0 to 100.0 wt. %, based on theamount of the by-product in the first mixture 101. The lower limit onthe amount of by-product removed from the first mixture 101 may be 5.0wt. %, 10.0 wt. %, 20.0 wt. %, 30.0 wt. %, 40.0 wt. %, 50.0 wt. %, 55.0wt. %, 60.0 wt. %, 65.0 wt. %, 70.0 wt. %, 75.0 wt. %, 80.0 wt. %, 85.0wt. %, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %. The upperlimit on the amount of by-product removed from the first mixture 101 maybe 5.0 wt. %, 10.0 wt. %, 20.0 wt. %, 30.0 wt. %, 40.0 wt. %, 50.0 wt.%, 55.0 wt. %, 60.0 wt. %, 65.0 wt. %, 70.0 wt. %, 75.0 wt. %, 80.0 wt.%, 85.0 wt. %, 90.0 wt. %, 95.0 wt. %, 99.0 wt. %, or 100.0 wt. %. Anycombination of lower and upper limits on the amount of by-productremoved from the first mixture 101 is expressed disclosed. In particularaspects, the by-product removed via line 303 is o-xylene. In anotheraspect, the by-product comprises one or more C₉₊ aromatic compounds. Inparticular aspects, the portion of the C₈₊ hydrocarbons provided tostage 301, e.g., via line 204, comprises ≧50.0 wt. %, ≧55.0 wt. %, ≧60.0wt. %, ≧65.0 wt. %, ≧70.0 wt. %, ≧75.0 wt. %, ≧80.0 wt. %, ≧85.0 wt. %,≧90.0 wt. %, ≧95.0 wt. %, ≧99.0 wt. %, p-xylene. Optional fourthseparation stage will now be described in more detail.

Fourth separation stage 304 may be any suitable separation means, e.g.,distillation tower, stabilization tower, flash drum, etc. At least aportion of the reactor effluent comprising the C₈₊ hydrocarbonsseparated in second separation stage 201 via line 203 may be provided tofourth separation stage 304, for removing and conducting away from theprocess at least a portion of one or more of toluene, o-xylene or C₉₊aromatics. A p-xylene containing portion exits third separation stage304 via a stream 306, which may be further processed or purified. Inparticular aspects at least a portion of p-xylene containing stream 306may be recycled as described for streams 203 and 204.

FIG. 4 illustrates a process 400 encompassing aspects of the invention.First mixture 401, comprising ethylbenzene, p-xylene, m-xylene, ando-xylene may be provided to optional distillation column 402. Optionaldistillation column 402 separates an ethylbenzene containing distillate403 comprising p-xylene and m-xylene and a residue 404 comprisingxylenes and a minor amount of ethylbenzene. In particular aspects,however, distillation tower 402 may be absent. In certain aspects wheredistillation column 402 is absent, first mixture 401 may be provideddirectly to distillation tower 409 or to first simulated moving bedabsorptive separation column 418.

In aspects utilizing distillation tower 402, residue 404 is provided todistillation tower 409. Optional distillation tower 409 may be anyseparation means suitable for at least partially separating o-xylenefrom the residue 404. In particular aspects, distillation tower 409 maybe a xylene splitter. Optionally, residue 404 may be combined withisomerate from isomerization reactor 427 described below.

Distillation tower 409 delivers a distillate through a line 410comprising an increased concentration of the m-xylene and p-xylene,based on the concentration of these compounds as provided to thedistillation tower 409. A residue comprising o-xylene exits thedistillation tower 409 via line 411.

The o-xylene in line 411 is further isolated in a distillation column412 from which o-xylene-containing distillate is removed from line 413.At least a portion of the o-xylene exiting the distillation tower 412via line 413 may be recycled to an isomerization reactor 427 or carriedaway from the process for further isolation or processing. A residuecontaining C₉₊ hydrocarbons exits distillation tower 409 via line 415.

Distillate is provided to a first simulated moving bed absorptiveseparation column 418 having a desorbent, e.g., toluene, introducedtherein from an external source (not shown) and recycled through column418 via line 418 a. A p-xylene containing portion is typically withdrawnalong with desorbent via line 419. The p-xylene in line 419 may bedirected to a distillation column 421 to separate the desorbent as adistillate fraction which is combined via line 421 a with the desorbentin line 423 for recycle to stage 418. The p-xylene recovered as residueby line 422 generally has a high purity, e.g., 99.8%, or otherwisepurified in at least one crystallization zone 417 at high temperature,as described European Patent EP-B-531 191, incorporated herein byreference in its entirety. The p-xylene conducted away via line 424generally has a purity greater than 99.9%, for example. A liquid streamobtained from crystallization zone 417 can be withdrawn via line 416,combined the xylene-containing distillate in line 410 and provided tothe first simulated moving bed absorptive separation stage 418.

An ethylbenzene-containing portion as described above is withdrawn fromthe column 418 via line 420, and is preferably removed from the process.Non-aromatics can be removed in stage 418 and conducted away (notshown).

A p-xylene depleted raffinate as described above is withdrawn from thecolumn 418 via line 425. This raffinate typically comprises toluene andm-xylene. The raffinate of line 425 is combined with the o-xylene-richline 413, and introduced into isomerization reactor 427 via line 426. Inparticular aspects the p-xylene depleted raffinate in line 426 comprises<10 wt. % ethylbenzene and >10 wt. % toluene, based on the total weightof the components in line 426.

Isomerization reactor 427 may be any suitable reactor for isomerizingxylene/ethylbenzene mixtures. In particular aspects, the reactor 427comprises a liquid phase isomerization process including a fixed bed ofa zeolitic catalyst such as ZSM-5, under isomerization conditions theincrease the content of p-xylene therein, preferably operated in theabsence of hydrogen at a space velocity of 3 hr⁻¹, for example, at atemperature of about 260° C. and a pressure <30 bar.

This reactor effluent exits the reactor 427 and is introduced into adistillation column 428 (for example a distillation column comprisingabout 30 plates). Distillation column 428 separates the reactor effluentinto a light fraction (e.g., C₁-C₇ hydrocarbon, particularly C₁-C₇non-aromatic hydrocarbon) recovered by a line 429, a toluene fractionrecycled by a line 430 to the adsorption column 418, and axylene-enriched raffinate that is provided to distillation tower 409 vialine 431. Optionally, residue 404 may be combined with distilledisomerate from the isomerization reactor 427.

Typically, the xylene-enriched raffinate 431 comprises p-xlene as themajor isomer. A typical concentration of xylene isomers correspondingcomprises 15 to 30 wt. % p-xylene, 10 to 30 wt. % o-xylene and 40 to 60wt. % m-xylene. Typically, ethylbenzine comprises about 10 wt. % of thexylene-enriched raffinate.

Optionally, distillate 403 comprising p-xylene and m-xylene from thedistillation column 402 may be fed, optionally in combination withethylbenzene provided via line 420, to a catalytic vapor-phaseisomerization reactor 432 of operating e.g., at a temperature of about370-400° C. In aspects utilizing line 420, ethylbenzene conveyed vialine 420 can be obtained from an external source (not shown). Typically,the distillate 403 comprises ≦10.0 wt. %, e.g., ≦7.5.0 wt. %, ≦5.0 wt.%, ≦2.5 wt. %, ≦1.0 wt. %, of the aromatic C₈ isomers in the xyleneloop, based on the weight of aromatic C₈ isomers in the xylene loop. Theresulting isomerate conducted away from stage 432 is enriched in xylene,and may be passed to separation stage 405. Light hydrocarbons i.e.,C₁-C₇ hydrocarbons are separated and carried away form the process vialine 407, optionally combined with the light hydrocarbons of line 429.Benzene and toluene may be separated from the isomerate, and optionallycarried away from the process, via line 406. Isomerization effluentexits the separation stage 405 may be combined with the first mixture401 and provided to the distillation column 402.

Particular Aspects

Additionally or alternately, the present invention can include one ormore of the following embodiments. The invention is not limited to theseembodiments, and this description is not meant to foreclose otherembodiments within the broader scope of the invention.

Embodiment 1. A process for producing p-xylene, the process comprising,(a) providing a first mixture comprising ≧5.0 wt. % of aromatic C₈isomers, based on the weight of the first mixture, said C₈ isomerscomprising p-xylene and ethylbenzene; (b) separating from the firstmixture in a first separation stage one or more of (i) ap-xylene-containing portion, (ii) a non-aromatics containing portion,and (iii) an ethylbenzene-containing portion, to form ap-xylene-depleted raffinate, wherein the first separation stage includesat least one simulated moving-bed adsorptive separation stage; (c)reacting at least a portion the p-xylene-depleted raffinate in theliquid phase to produce a reactor effluent comprising aromatic C₈isomers; and (d) combining with the first mixture ≧50.0 wt. %,preferably ≧90.0 wt. %, of the reactor effluent's aromatic C₈ isomers,preferably p-xylene, based on the weight of the reactor effluent'saromatic C₈ isomers, the combining being carried out before and/orduring the separating of (b).

Embodiment 2. The process of Embodiment 1, wherein the separating step(b) includes separating from the first mixture: (A) thep-xylene-depleted raffinate; (B) the p-xylene-containing portioncomprising ≧10.0 wt. % of the first mixture's p-xylene, based on theweight of the first mixture's p-xylene; and (C) theethylbenzene-containing portion comprising ≧10.0 wt. % of the firstmixture's ethylbenzene, based on the weight of the first mixture'sethylbenzene.

Embodiment 3. The process of Embodiment 1 or 2, further includingconducting away at least a portion of the p-xylene-containing portion.

Embodiment 4. The process of any of Embodiments 1 to 3, furtherincluding conducting away ≧50.0 wt. % of the ethylbenzene-containingportion, based on the weight of the separated ethylbenzene.

Embodiment 5. The process of any of Embodiments 1 to 4, wherein thefirst mixture comprises ≧50.0 wt. % of a mixture of p-xylene,ethylbenzene, m-xylene, and o-xylene, based on the weight of the firstmixture.

Embodiment 6. The process of any of Embodiments 1 to 5, wherein thefirst mixture comprises about 12 wt. % to 32 wt. %, particularly 17 wt.% to 27 wt. % or 20.0 wt. % to 25.0 wt. %, p-xylene; 35 wt. % to 55 wt.%, particularly 40 wt. % to 50 wt. % or 42.5 wt. % to 47.7 wt. %,m-xylene; 13 wt. % to 33 wt. %, particularly 18 wt. % to 28 wt. % or20.0 wt. % to 25.0 wt. % o-xylene; and 1.0 wt. % to 20.0 wt. %,particularly 5.0 wt. % to 15.0 wt. % or 7.5 wt. % to 12.5 wt. %,ethylbenzene.

Embodiment 7. The process of any of Embodiments 1 to 6, wherein reactingat least a portion the p-xylene-depleted raffinate in the liquid phaseincludes at least one of (i) one or more reforming reactions, (ii) oneor more disproportionation reactions, (iii) one or more transalkylationreactions, and (iv) one or more cracking reactions.

Embodiment 8. The process of any of the Embodiments encompassed byEmbodiment 7, further comprising: (e) separating from the reactoreffluent in a second separation stage at least a portion of any C₁-C₇compounds produced during the reacting step (c), the step (e) beingcarried out before the combining step (d); and (f) conducting theseparated C₇ compounds away from the process.

Embodiment 9. The process of any of Embodiments 1 to 8, wherein theprocess further comprises: (g) removing a by-product from the firstmixture, the by-product comprising (1) at least a portion of the firstmixture's o-xylene and/or (2) at least a portion of any C₉₊ aromatics inthe first mixture; and/or (h) separating from the reactor effluent in athird separation stage one or more of toluene, o-xylene or C₉₊aromatics, and conducting away at least a portion of one or more of theseparated toluene, the separated o-xylene, and the separated C₉₊aromatics.

Embodiment 10. The process of any of the Embodiments encompassed byEmbodiment 9, further comprising separating from the first mixture inthe first separation stage ≧50.0 wt. %, preferably ≧75.0 wt. %, or ≧90.0wt. %, of any non-aromatic hydrocarbon molecules.

Embodiment 11. The process of any of Embodiments 1-10, wherein thereacting of step (c) includes liquid-phase isomerization, and wherein≦10.0 wt. % of the p-xylene-depleted raffinate is in the vapor phaseduring the reacting, the weight percent being based on the weight of thep-xylene-depleted raffinate.

Embodiment 12. The process of Embodiment 11, wherein ≦1.0 wt. %,preferably ≦0.1 wt. %, of the p-xylene-depleted raffinate is in thevapor phase during the reacting.

Embodiment 13. The process of any of Embodiments 1-12, wherein (i) ≧90.0wt. % of the first mixture's ethylbenzene is separated bychromatographic separation in the first separation stage, (ii) ≧90.0 wt.% of the separated ethylbenzene is conducted away from the process, and(iii) ≧90.0 wt. % of the reactor effluent's aromatic C₈ isomers arecombined with the first mixture in step (d).

Embodiment 14. In a xylene loop, wherein the xylene loop comprises (a)providing a first mixture comprising aromatic C₈ isomers; (b) separatingfrom the first mixture in a first stage: (i) a p-xylene-depletedraffinate; (ii) a p-xylene-containing portion comprising ≧10.0 wt. % ofthe mixture's p-xylene, based on the weight of the mixture's p-xylene;and at least one of (iii) an ethylbenzene-containing portion comprising≧10.0 wt. % of the first mixture's ethylbenzene, based on the weight ofthe first mixture's ethylbenzene; or (iv) ≧10.0 wt. % of anynon-aromatics in the first mixture; wherein the first separation stageincludes at least one simulated moving-bed adsorption chromatographicseparation; (c) conducting away at least a portion of the separatedp-xylene; (d) reacting at least a portion the p-xylene-depletedraffinate in the liquid phase to produce a reactor effluent comprisingaromatic C₈ isomers; and (e) recycling to step (b) ≧50.0 wt. % ofaromatic C₈ isomers of the reactor effluent, based on the weight of thearomatic C₈ isomers in the reactor effluent; the improvement comprising:(f) conducting away from the xylene loop (i) ≧50.0 wt. % of theethylbenzene separated in step (c), based on the weight of the separatedethylbenzene, and/or (ii) ≧50.0 wt. % of any non-aromatics separated instep (c); and (g) exposing ≦10.0 wt. % of aromatic C₈ isomers in thexylene loop to vapor-phase isomerization, based on the weight ofaromatic C₈ isomers in the xylene loop.

Embodiment 15. The process of Embodiment 14, wherein the first mixturecomprises ≧50.0 wt. % of a mixture of p-xylene, ethylbenzene, m-xylene,and o-xylene, based on the weight of the first mixture.

Embodiment 16. The process of Embodiment 14 or 15, wherein the firstmixture comprises about 12 wt. % to 32 wt. %, particularly 17 wt. % to27 wt. % or 20.0 wt. % to 25.0 wt. %, p-xylene; 35 wt. % to 55 wt. %,particularly 40 wt. % to 50 wt. % or 42.5 wt. % to 47.7 wt. %, m-xylene;13 wt. % to 33 wt. %, particularly 18 wt. % 28 wt. %, or 20.0 wt. % to25.0 wt. % o-xylene; and 1.0 wt. % to 20.0 wt. %, particularly 5.0 wt. %to 15.0 wt. % or 7.5 wt. % to 12.5 wt. %, ethylbenzene.

Embodiment 17. The process of any of Embodiments 14 to 16, whereinreacting at least a portion the p-xylene-depleted raffinate in theliquid phase includes at least one of (i) one or more reformingreactions, (ii) one or more disproportionation reactions, (iii) one ormore transalkylation reactions, and (iv) one or more cracking reactions.

Embodiment 18. The process of any of Embodiments 14 to 17, furthercomprising: (h) separating from the reactor effluent in a secondseparation stage at least a portion of any C₁-C₇ compounds producedduring the reacting step (c), the step (e) being carried out before thecombining step (d); and (i) conducting the separated C₁-C₇ compoundsaway from the process.

Embodiment 19. The process of any of Embodiments 14 to 18, wherein theprocess further comprises: (j) removing a by-product from the firstmixture, the by-product comprising (1) at least a portion of the firstmixture's o-xylene and/or (2) at least a portion of any C₉₊ aromatics inthe first mixture; and/or (k) separating from the reactor effluent in athird separation stage one or more of toluene, o-xylene or C₉₊aromatics, and conducting away at least a portion of one or more of theseparated toluene, the separated o-xylene, and the separated C₉₊aromatics.

Embodiment 20. The process of any embodiment encompassed by Embodiment19, further comprising separating from the first mixture in the firstseparation stage ≧50.0 wt. %, preferably ≧75.0 wt. %, or ≧90.0 wt. %, ofany non-aromatic hydrocarbon molecules.

Embodiment 21. The process of any of Embodiments 14 to 20, wherein thereacting of step (d) includes liquid-phase isomerization, and wherein≦10.0 wt. % of the p-xylene-depleted raffinate is in the vapor phaseduring the reacting, the weight percent being based on the weight of thep-xylene-depleted raffinate.

Embodiment 22. The process of any embodiment encompassed by Embodiment20, wherein ≦1.0 wt. %, preferably ≦0.1 wt. %, of the p-xylene-depletedraffinate is in the vapor phase during the reacting.

Embodiment 23. The process of any of Embodiments 14 to 22, wherein (i)≧90.0 wt. % of the first mixture's ethylbenzene is separated bychromatographic separation in the first separation stage, (ii) ≧90.0 wt.% of the separated ethylbenzene is conducted away from the process, and(iii) ≧90.0 wt. % of the reactor effluent's aromatic C8 isomers arecombined with the first mixture in step (d).

Embodiment 24. A process for producing p-xylene, the process comprising,(a) providing a first mixture comprising ≧5.0 wt. % of aromatic C₈isomers, based on the weight of the first mixture, said C₈ isomerscomprising p-xylene and ethylbenzene; (b) separating from the firstmixture in a first separation stage wherein the first separation stageincludes at least one simulated moving-bed adsorptive separation stage:(i) a p-xylene-depleted raffinate; (ii) a p-xylene-containing portioncomprising ≧10.0 wt. % of the first mixture's p-xylene, based on theweight of the first mixture's p-xylene; and (iii) anethylbenzene-containing portion comprising ≧10.0 wt. % of the firstmixture's ethylbenzene, based on the weight of the first mixture'sethylbenzene; (c) conducting away at least a portion of thep-xylene-containing portion; (d) conducting away ≧50.0 wt. % of theethylbenzene-containing portion, based on the weight of theethylbenzene-containing portion; (e) isomerizing at least a portion thep-xylene-depleted raffinate in the liquid phase wherein ≦10.0 wt. %,e.g., ≦1.0 wt. % or 0.1 wt. %, of the p-xylene-depleted raffinate is inthe vapor phase during the isomerizing, the weight percent being basedon the weight of the p-xylene-depleted raffinate, to produce a reactoreffluent comprising ≧90.0 wt. % p-xylene, based on the weight of thereactor effluent's aromatic C₈ isomers; and (f) combining with the firstmixture at least a portion of the reactor effluent, the combining beingcarried out before and/or during the separating of (b).

Embodiment 25. The process of Embodiment 24, further comprising: (g)removing a by-product from the first mixture, the by-product comprising(1) at least a portion of the first mixture's o-xylene and/or (2) atleast a portion of any C₉₊ aromatics in the first mixture; and/or (h)separating from the reactor effluent in a third separation stage one ormore of toluene, o-xylene or C₉₊ aromatics, and conducting away at leasta portion of one or more of the separated toluene, the separatedo-xylene, and the separated C₉₊ aromatics; and wherein step (b) furtherincludes (iv) a non-aromatic hydrocarbon portion, comprising ≧50.0 wt.%, preferably ≧75.0 wt. %, or ≧90.0 wt. %, of the first mixture'snon-aromatic hydrocarbon molecules.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining theenforceable scope of the present invention.

As demonstrated above, aspects of the invention provide methods ofmaking p-xylene, particularly in a xylene loop. The new methods have oneor more of the following advantages. For example, the vapor-phaseisomerization stage may be further reduced in size when non-aromaticsare separated and conducted away from the xylene loop upstream ofisomerization. Vapor-phase isomerization stage(s) can be eliminatedaltogether when substantially all of the non-aromatics and substantiallyall of the ethylbenzene are separated and conducted away from the xyleneloop upstream of isomerization. An advantage of some aspects is that thesame type of chromatographic separation as is used for p-xylene andethylbenzene separation from a mixture of aromatic C₈ isomers can alsobe utilized for separating and removing non-aromatics from the loop,e.g., as a component of a third raffinate, upstream of the isomerizationstage. In the conventional process, vapor-phase isomerization is neededfor cracking these molecules into lower molecular weight fragments. Theinvention overcomes this difficulty because the sufficient non-aromaticsare conducted away from the xylene loop as a component of the thirdraffinate. Other characteristics and additional advantages are apparentto those skilled in the art.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents and/or testing procedures to the extent they arenot inconsistent with this text. As is apparent from the foregoinggeneral description and the specific embodiments, while forms of theinvention have been illustrated and described, various modifications canbe made without departing from the spirit and scope of the invention.Accordingly, it is not intended that the invention be limited thereby.Likewise, the term “comprising” is considered synonymous with the term“including”. Likewise whenever a composition, an element or a group ofelements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A process for producing p-xylene, the processcomprising: (a) providing a first mixture comprising ≧5.0 wt. % ofaromatic C₈ isomers, the C₈ isomers comprising p-xylene andethylbenzene; (b) separating from the first mixture in a firstseparation stage a p-xylene-containing portion and (i) anethylbenzene-containing portion and/or (ii) a non-aromatic containingportion, to form a p-xylene-depleted raffinate; (c) reacting at least aportion the p-xylene-depleted raffinate in the liquid phase to produce areactor effluent comprising aromatic C₈ isomers; (d) combining with thefirst mixture ≧50.0 wt. % of the reactor effluent's aromatic C₈ isomers,the combining being carried out before and/or during the separating of(b), and (e) conducting away at least part of the separatedethylbenzene-containing portion and/or conducting away at least part ofthe separated non-aromatic containing portion.
 2. The process of claim1, wherein the separating step (b) includes separating from the firstmixture: i. the p-xylene-containing portion comprising ≧10.0 wt. % ofthe first mixture's p-xylene; and ii. the ethylbenzene-containingportion comprising ≧10.0 wt. % of the first mixture's ethylbenzene. 3.The process of claim 1, further including conducting away at least aportion of the separated p-xylene-containing portion.
 4. The process ofclaim 1, further including conducting away ≧50.0 wt. % of the separatedethylbenzene-containing portion.
 5. The process of claim 1, wherein thefirst mixture comprises ≧50.0 wt. % of a mixture of p-xylene,ethylbenzene, m-xylene, and o-xylene.
 6. The process of claim 1, whereinthe first mixture comprises 17 wt. % to 27 wt. % p-xylene, 40 wt. % to50 wt. % m-xylene, 18 wt. % to 28 wt. % o-xylene, and 5 wt. % to 15 wt.% ethylbenzene.
 7. The process of claim 1, wherein the reacting at leasta portion the p-xylene-depleted raffinate in the liquid phase includesat least one of (i) one or more reforming reactions, (ii) one or moredisproportionation reactions, (iii) one or more transalkylationreactions, and (iv) one or more cracking reactions.
 8. The process ofclaim 1, further comprising: (f) separating from the reactor effluent ina second separation stage at least a portion of any C₁-C₇ compoundsproduced during the reacting step (c), the step (e) being carried outbefore the combining step (d); and (g) conducting the separated C₁-C₇compounds away from the process.
 9. The process claim 8, wherein theprocess further comprises: (h) removing from the first mixture (1) atleast a portion of any o-xylene and/or (2) at least a portion of any C₉₊aromatics; and/or (i) separating from the reactor effluent in a thirdseparation stage one or more of toluene, o-xylene or C₉₊ aromatics, andconducting away at least a portion of one or more of the separatedtoluene, the separated o-xylene, and the separated C₉₊ aromatics. 10.The process of claim 1, further comprising conducting away ≧50.0 wt. %of the non-aromatic containing portion separated in step (b), based onthe total weight of the separated non-aromatic portion.
 11. The processof claim 1, wherein the reacting of step (c) includes liquid-phaseisomerization, and wherein ≦10.0 wt. % of the p-xylene-depletedraffinate is in the vapor phase during the reacting.
 12. The process ofclaim 1, wherein ≦1.0 wt. % of the p-xylene-depleted raffinate is in thevapor phase during the reacting.
 13. The process of claim 1, wherein (i)≧90.0 wt. % of the first mixture's ethylbenzene is separated bychromatographic separation in the first separation stage, (ii) ≧90.0 wt.% of the separated ethylbenzene is conducted away from the process, and(iii) ≧90.0 wt. % of the reactor effluent's aromatic C₈ isomers arecombined with the first mixture in step (d).
 14. In a xylene loop,wherein the xylene loop comprises (a) providing a first mixturecomprising aromatic C₈ isomers; (b) separating from the first mixture ina first stage: (i) a p-xylene-depleted raffinate; (ii) ap-xylene-containing portion comprising ≧10.0 wt. % of the mixture'sp-xylene; and (iii) an ethylbenzene-containing portion comprising ≧10.0wt. % of the mixture's ethylbenzene; wherein the first separation stageincludes at least one simulated moving-bed adsorption chromatographicseparation; (c) conducting away at least a portion of the separatedp-xylene; (d) reacting at least a portion the p-xylene-depletedraffinate in the liquid phase to produce a reactor effluent comprisingaromatic C₈ isomers; (e) recycling to step (b) ≧50.0 wt. % of aromaticC₈ isomers of the reactor effluent; the improvement comprising: (f)conducting away from the xylene loop ≧50.0 wt. % of the ethylbenzeneseparated in step (b); and (g) exposing ≦10.0 wt. % of aromatic C₈isomers in the xylene loop to vapor-phase isomerization.
 15. The processof claim 14, wherein the first mixture comprises ≧50.0 wt. % of amixture of p-xylene, ethylbenzene, m-xylene, and o-xylene.
 16. Theprocess of claim 14, wherein the first mixture comprises about 17 wt. %to 27 wt. % p-xylene, 40 wt. % to 50 wt. % m-xylene, 18 wt. % to 28 wt.% o-xylene, and 5 wt. % to 15 wt. % ethylbenzene.
 17. The process ofclaim 14, wherein reacting at least a portion the p-xylene-depletedraffinate in the liquid phase includes at least one of (i) one or morereforming reactions, (ii) one or more disproportionation reactions,(iii) one or more transalkylation reactions, and (iv) one or morecracking reactions.
 18. The process of claim 14, further comprising: (h)separating from the reactor effluent in a second separation stage atleast a portion of any C₁-C₇ compounds produced during the reacting step(d); and (i) conducting the separated C₁-C₇ compounds away from theprocess.
 19. The process of claim 18, wherein the process furthercomprises: (j) removing from the first mixture (1) at least a portion ofany o-xylene and/or (2) at least a portion of any C₉₊ aromatics; and/or(k) separating from the reactor effluent in a third separation stage oneor more of toluene, o-xylene or C₉₊ aromatics, and conducting away atleast a portion of one or more of the separated toluene, the separatedo-xylene, and the separated C₉₊ aromatics.
 20. The process of claim 14,further comprising separating from the first mixture in the firstseparation stage ≧50.0 wt. % of any non-aromatic hydrocarbon molecules.21. The process of claim 14, wherein the reacting of step (d) includesliquid-phase isomerization, and wherein ≦10.0 wt. % of thep-xylene-depleted raffinate is in the vapor phase during the reacting.22. The process of claim 14, wherein ≦1.0 wt. % of the p-xylene-depletedraffinate is in the vapor phase during the reacting.
 23. The process ofclaim 14, wherein (i) ≧90.0 wt. % of the first mixture's ethylbenzene isseparated by chromatographic separation in the first separation stage,(ii) ≧90.0 wt. % of the separated ethylbenzene is conducted away fromthe process, and (iii) ≧90.0 wt. % of the reactor effluent's aromatic C₈isomers are combined with the first mixture in step (d).
 24. A processfor producing p-xylene, the process comprising, (a) providing a firstmixture comprising ≧5.0 wt. % of aromatic C₈ isomers, said C₈ isomerscomprising p-xylene and ethylbenzene; (b) separating from the firstmixture in a first separation stage wherein the first separation stageincludes at least one simulated moving-bed adsorptive separation stage:i. a p-xylene-depleted raffinate; ii. a p-xylene-containing portioncomprising ≧10.0 wt. % of the first mixture's p-xylene; and iii. anethylbenzene-containing portion comprising ≧10.0 wt. % of the firstmixture's ethylbenzene; (c) conducting away at least a portion of thep-xylene-containing portion; (d) conducting away ≧50.0 wt. % of theethylbenzene-containing portion; (e) isomerizing at least a portion thep-xylene-depleted raffinate in the liquid phase wherein ≦10.0 wt. %,e.g., ≦1.0 wt. % or ≦0.1 wt. %, of the p-xylene-depleted raffinate is inthe vapor phase during the isomerizing, to produce a reactor effluentcomprising ≧90.0 wt. % p-xylene; and (f) combining with the firstmixture at least a portion of the reactor effluent, the combining beingcarried out before and/or during the separating of (b).
 25. The processof claim 24, further comprising: (g) removing from the first mixture (1)at least a portion of any o-xylene and/or (2) at least a portion of anyC₉₊ aromatics; and/or (h) separating from the reactor effluent in athird separation stage one or more of toluene, o-xylene or C₉₊aromatics, and conducting away at least a portion of one or more of theseparated toluene, the separated o-xylene, and the separated C₉₊aromatics; and wherein the separating of step (b) further includes (iv)a non-aromatic hydrocarbon portion, comprising ≧50.0 wt. %, of the firstmixture's non-aromatic hydrocarbon molecules.